JPH045539B2 - - Google Patents

Description

[Detailed description of the invention]

(Industrial Application Field) The present invention is used for building materials such as flooring materials, wall materials, vehicle seats, bags, bags, furniture, etc., in which the printed pattern matches the uneven pattern and the surface is delicate and sharp. The present invention relates to a method for manufacturing an embossed sheet having a pattern and excellent decorative properties. (Prior art) As a method for manufacturing an embossed sheet with a matching printed pattern and uneven pattern as described above, printing ink containing a foaming suppressor and/or foaming accelerator is printed on the surface of a foamable synthetic resin layer, There is a chemical embossing method in which this is foamed to create an uneven pattern, and a synchronized embossing method in which an embossing roll is used to emboss according to the printed pattern, but in the chemical embossing method, the uneven pattern of the printed pattern is matched. However, it is impossible to express sharp unevenness with fibers. Also, in the case of synchronized embossing, it is possible to express sharp unevenness with fibers depending on the shape of the embossing roll used, but it is not possible to express sharp unevenness with fibers, but it is impossible to express sharp unevenness with fibers. Due to expansion and contraction of the sheet, machine conditions, etc., it was difficult to match the patterns, resulting in very poor workability and a high incidence of defects. (Means for solving the problems) The present invention forms a layer of a foamable vinyl chloride resin composition on a base material, prints an arbitrary pattern on the surface with a printing ink containing a foam suppressing material, and A transparent or translucent vinyl chloride resin layer is formed on top of the resin layer, then heated and foamed to reveal an uneven pattern, and an embossing roll with an arbitrary design applied to the surface is used to form a squeeze pattern. In the method for producing a synchronized embossed sheet with a matching uneven pattern, the average degree of polymerization of the vinyl chloride resin used in the layer of the foamable vinyl chloride resin composition is 1200 or more, and the vinyl chloride resin is transparent or translucent. The average degree of polymerization of the vinyl chloride resin used in the layer is 100 or more higher than the average degree of polymerization of the vinyl chloride resin used in the layer of the foamable vinyl chloride resin composition, and the expansion ratio is 4 times or less. The present invention relates to a method for manufacturing a synchronized embossed sheet. The base materials used in the present invention include one or more types of inorganic or organic fibers such as natural animal or vegetable fibers, asbestos, glass fibers, rock wool, pulp, and synthetic fibers, and if necessary, calcium carbonate.
Other releasable carriers such as woven fabrics, knitted fabrics, non-woven fabrics, and paper mixed with clay, fillers such as aluminum hydroxide, and resin binders can be used, and these can be used freely depending on the intended use of the product. It is possible. In addition to the above, a foamed or non-foamed synthetic resin sheet may be laminated on the back surface of the woven fabric, knitted fabric, nonwoven fabric, paper, etc. (the surface opposite to the surface on which the layer of the foamable synthetic resin composition is formed). can also be used as a base material for the tuned embossed sheet of the present invention. The layer of the foamable vinyl chloride resin composition is composed of a vinyl chloride resin, a chemical blowing agent that decomposes when heated to generate gas, and a foaming aid that accelerates the decomposition of the blowing agent, and may contain other ingredients as necessary. Commonly used additives such as plasticizers, stabilizers, fillers, fungicides, viscosity reducers, and colorants are used. The vinyl chloride resin mentioned above refers to polyvinyl chloride resin, vinyl chloride, and other monomers such as ethylene,
It includes copolymers with vinyl acetate, vinyl ether, maleic ester, acrylic, urethane, etc., as well as blends of polyvinyl chloride resin and other polymers, and the average degree of polymerization of the vinyl chloride resin used is 1200. It is necessary that it is above. If the average degree of polymerization of the vinyl chloride resin is less than 1200, the melt viscosity of the foam layer will be low during heat embossing, and the pressure of the embossing roll will destroy the foam cells, causing roughness on the surface, making embossing difficult. be. Note that the average degree of polymerization used in the present invention refers to the degree of polymerization of vinyl chloride resins generally supplied on the market, and refers to the degree of polymerization of vinyl chloride resins that are generally supplied on the market. It is the average degree of polymerization of individual molecules in the resin. In the present invention, if one type of vinyl chloride resin is used, it means the average degree of polymerization of that resin, and if a blend of multiple types of resins with different average degrees of polymerization is used, the following will be used. As shown in the examples, it means the arithmetic mean value taking into account the blending ratio of each resin. As the blowing agent, commonly used ones can be used, but azodicarbonamide is particularly preferred. The amount added is preferably 0.5 to 5 parts by weight per 100 parts by weight of vinyl chloride resin. The foaming aid that accelerates the decomposition of the foaming agent can be one that is normally used depending on the type of foaming agent, but when using azodicarbonamide as the foaming agent, zinc-based or lead-based foaming agents such as zinc acetate can be used. A foaming aid that also serves as a stabilizer is preferred. Plasticizers include dibutyl phthalate, diisobutyl phthalate, dioctyl phthalate, didodecyl phthalate, butylbenzyl phthalate, diisodecyl phthalate, dihexyl phthalate,
Didodecyl phthalate, diisononyl phthalate, dioctyl adipate, diisodecyl adipate, dibutyl sebacate, dioctyl sebacate, tributyl phosphate, tricresyl phosphate, triphenyl phosphate, trichloroethyl phosphate, trioctyl phosphate, diphenyl cresyl In addition to phosphates, common plasticizers such as trimellitic acid ester plasticizers, epoxy plasticizers such as epoxidized soybean oil and various epoxy resins, and polyester polymer plasticizers can be used. In addition, when using a vinyl chloride resin paste as a foamable vinyl chloride resin composition, gasoline, octane,
Commonly used diluents such as benzene, toluene, naphtha, and dodecylbenzene derivatives, secondary plasticizers, viscosity reducing agents, etc. are used in combination with the plasticizer. The amount of the plasticizer added is preferably 20 to 100 parts by weight per 100 parts by weight of the vinyl chloride resin, 1 to 20 parts by weight of the diluent and secondary plasticizer, and 0.1 to 5 parts by weight of the viscosity reducing agent. . As the stabilizer, commonly used stabilizers can be used, but when azodicarbonamide is used as a foaming agent, it is preferable to use zinc-based or lead-based materials such as zinc oxide, which have the effect of acting as a foaming aid and stabilizer. . The amount of the stabilizer added is preferably in the range of 0.5 to 7 parts by weight per 100 parts by weight of the vinyl chloride resin. Any filler can be used as long as it does not undergo physical or chemical changes such as melting or decomposition at the processing temperature, including calcium carbonate, magnesium carbonate, clay, talc, silica, diatomaceous earth, silica sand, Pumice powder, flake powder, mica powder, asbestos,
Inorganic fillers such as aluminum hydroxide, aluminum oxide, aluminum sulfate, barium sulfate, calcium sulfate, glass bulbs, foamed glass bulbs, fly ash bulbs, volcanic glass hollow bodies (shirasu balloons), powdered cellulose (cellulose powder), polyvinyl alcohol Organic fillers such as fiber, cork powder, wood flour, thermosetting resin powder, thermosetting resin hollow spheres, etc. can be used. The amount of the filler added is preferably in the range of 5 to 400 parts by weight per 100 parts by weight of the vinyl chloride resin. As a fungicide, commonly used ones can be used, but among them, 10,10'-oxybisphenoxial, which does not sometimes discolor vinyl chloride resin or inhibit the foaming suppressing effect of foaming inhibitors, can be used. Syn, N(-fluorodichloromethylthio-)phthalimide, N-trichloromethylmercapto-
Organic fungicides such as 4-cyclohexene-1,2-dicarboximide and 2,4,5,6-tetrachloroisophthalonitrile are added to vinyl chloride resin 100%.
When 0.1 to 5 parts by weight is required to maintain the effect, it is preferable to use 1 to 30 parts by weight of an inorganic antifungal agent such as barium metaborate. Of course, the above antifungal agents can be used alone or in combination of two or more. The printing ink used in the present invention can be any commonly used printing ink. however,
At least one color of the printing ink for printing the pattern must contain a commonly used foaming inhibitor such as trimellitic anhydride and dithiocyanuric acid derivatives to suppress foaming of the foamable vinyl chloride resin layer and form recesses. It is necessary. The amount of the foaming inhibitor added is appropriately adjusted depending on the desired depth of the concave portion, but is preferably in the range of 1 to 30% by weight based on the printing ink. As the transparent or translucent vinyl chloride resin layer of the present invention, any commonly used vinyl chloride resin composition can be used. In terms of the reproducibility of the embossed pattern by the embossing roll (embossing suitability) and the foaming suppressing effect of the foaming inhibitor, the lower the average degree of polymerization of the vinyl chloride resin used, the lower the heat melt viscosity of the resin and the easier it is to process. However, as shown in Comparative Example 2 below, if the degree of polymerization is lower than the average polymerization degree of the foamable vinyl chloride resin, it becomes transparent or translucent due to the influence of the decomposed gas of the blowing agent during foaming. A clear printed pattern cannot be obtained due to the significant generation of air bubbles at the interface between the vinyl chloride resin layer and the foamed vinyl chloride resin layer (i.e., the printing surface). In addition, as understood from Comparative Example 2 above and the Examples described later, the average degree of polymerization of the vinyl chloride resin used for the transparent or translucent vinyl chloride resin layer is also important from the viewpoint of improving surface smoothness. is required to be 100 or more higher than the average degree of polymerization of the vinyl chloride resin used in the layer of the foamable vinyl chloride resin composition. Incidentally, when the average degree of polymerization of the vinyl chloride resin increases, the heat-melt viscosity of the resin increases and the processability becomes poor. Therefore, in consideration of achieving proper embossing and the effect of suppressing foaming, it is preferably 4000 or less. Other plasticizers, stabilizers, fillers or matting agents as necessary,
Commonly used additives such as antifungal agents, viscosity reducing agents, and coloring agents are used. The vinyl chloride resin and various additives used as necessary can be used in the same amounts as those used in the above-mentioned foamable vinyl chloride resin composition. However, the filler or matting agent used in the above-mentioned foamable vinyl chloride resin composition is 0.5 to 20 parts by weight per 100 parts by weight of the vinyl chloride resin.
Weight part can be used. If this amount exceeds 20 parts by weight, the vinyl chloride resin layer becomes opaque and the desired product cannot be obtained, which is undesirable. The tuned embossed sheet of the present invention is produced by forming a layer of a foamable vinyl chloride resin composition on the sheet-like base material described above by a conventional method such as a calendering method, an extrusion method, a laminating method, a paste coating method, etc. An arbitrary pattern is printed using a printing ink containing a foaming inhibitor in at least one color using a conventional method such as gravure printing, flexo printing, rotary screen printing, or silk screen printing, and the surface is transparent or semi-transparent. After forming a transparent vinyl chloride resin layer using a conventional method such as calendaring, extrusion, lamination, or paste coating,
The foamable vinyl chloride resin composition is heated and foamed at a temperature higher than the decomposition temperature of the blowing agent contained in the composition to obtain a sheet-like material whose printed pattern matches the uneven pattern. It is obtained by heat embossing using a patterned embossing roll. Embossing methods include heating and foaming in an off-line process where a foaming furnace and embossing machine are installed separately, and then reheating and embossing, and another method that performs foaming immediately after foaming using an in-line machine with an embossing device installed immediately after the foaming furnace. There are two methods for performing heat embossing, and either method is applicable.
When embossing is performed offline, the foam layer once formed has been completely cooled, so the pressure of the embossing roll will not destroy the foam cells and cause roughness on the surface. It is necessary to apply heating conditions that will not cause the decomposition foaming agent to decompose and cause secondary foaming, causing foam cell roughness.If embossing is performed in-line immediately after heating and foaming, the foam layer will be in a softened state. Therefore, as much as possible, only the back side (the side opposite to the embossed side) is cooled, and the undecomposed foaming agent remaining in the foam layer is cooled on the surface.
It is necessary to perform embossing by heating under conditions that do not cause subsequent foaming. Also, performing so-called clearance embossing, in which a gap is provided between the embossing roll and the rubber roll (backup roll) during embossing, is effective in preventing foam cell destruction in the foam layer. In this case, the clearance (gap) varies somewhat depending on the foaming ratio of the foam layer and the average degree of polymerization of the vinyl chloride resin forming the foam layer, so it is necessary to set it after checking each. In this case, the expansion ratio must be 4 times or less. The foaming ratio of the foam layer is 2.5 times or less, the average degree of polymerization of the vinyl chloride resin forming the foam layer is 1200 or more, the foam layer is heated under heating conditions that do not cause secondary foaming, and the pressure of the embossing roll is 2 to 2 times. By embossing at 3 Kg/cm ² (gauge pressure), the desired synchronous embossed sheet can be easily obtained without causing any problems such as destruction of the foam cells, even without providing the above-mentioned clearance. When the foaming ratio of the foam layer exceeds 2.5 times, it is preferable to provide a clearance as the foaming ratio increases. Note that the above-mentioned foaming ratio is the same as the foaming ratio generally used in this type of technology. That is,
Based on the thickness of the foamable vinyl chloride resin composition layer formed on the base material, it is expressed as how many times the original thickness the foamed layer becomes after heating and foaming it. For heating during embossing, it is preferable to use commonly used electric heaters, infrared or far infrared heaters, ceramic heaters, and the like. In addition, the embossing roll used here is one that has a squeezed pattern formed by mill pressing, and one that has been etched.
Any material can be used, such as those with a shibori pattern formed on it, those with a shibori pattern formed on it by electroforming, or those that have a shibori pattern formed on heat-resistant synthetic resin such as silicone resin, among others, those made from natural materials as they are. It is preferable to use an electroforming embossing roll or a roll made of synthetic resin such as silicone, which can produce a surface shape of
Furthermore, electroforming embossing rolls are preferred from the viewpoints of durability, shape retention (less changes in size and shape due to temperature changes), and cooling capability. (Operation and Effect) The present invention forms a layer of a foamable vinyl chloride resin composition on the surface of a base material, prints an arbitrary pattern on the surface with a printing ink containing a foaming inhibitor, and then prints a transparent layer on the surface. Alternatively, after forming a translucent vinyl chloride resin layer, it is heated and foamed to reveal an uneven pattern that matches the printed pattern, and then an embossing roll with a desired design on its surface is used to create a squeeze pattern using a heated embossing method. By forming this, it is possible to easily and economically produce a synchronized embossed sheet with a rich design, in which the printed pattern and the uneven pattern match, and furthermore, a fibrous and sharp drawing pattern is formed on the surface. In addition, the average degree of polymerization of the vinyl chloride resin used in the foamable vinyl chloride resin composition is 1200 or more, and it is used for a transparent or translucent vinyl chloride resin layer formed on the surface of the foamable vinyl chloride resin composition through a printed pattern. The average degree of polymerization of the vinyl chloride resin is 100 or more higher than the average degree of polymerization of the vinyl chloride resin used in the foamable vinyl chloride resin composition, and the expansion ratio is 4 times or less, During embossing using an embossing roll, the desired synchronous embossed sheet can be easily produced without problems such as foam cell destruction and surface roughening caused by the pressing of the embossing roll on the foam layer that is heated and softened or melted. be. Furthermore, the present invention is achieved by adding a design expression by a squeeze pattern made on an embossing roll to the design expression that perfectly matches the printed pattern and the uneven pattern by multicolor printing using printing ink partially containing a foaming inhibitor. , a sheet-like product with unprecedented complex and delicate decorative properties was obtained, which is suitable for use in building materials such as flooring and wall materials, vehicle seats, bags, bags, furniture, etc. be. Next, examples will be given to explain the present invention in more detail, but the present invention is not limited thereto. (Example) Examples 1 to 2, Comparative Example 1 Using a test coater with an effective mechanical width of 450 m/m, inorganic filler paper with a thickness of 0.95 m/m containing glass fiber, pulp, inorganic filler, and binder as main components was prepared. Using a doctor knife, apply the foamable vinyl chloride resin pastes () to () listed in Table 1 on the surface of the
The foamable vinyl chloride resin pastes () to () were applied to a thickness of 0.45 m/m and heated to gel by passing through a heating furnace set at 170°C at a speed of 2 m/min. Multicolor gravure printing with a wood grain pattern is applied to this surface (the joints corresponding to the joints between the wooden boards are printed with printing ink containing an inhibitor), and then
The transparent vinyl chloride resin paste () described in Table 1 was applied with a doctor knife to a thickness of 0.3 m/m, and passed through a heating furnace set at 170°C at a speed of 2 m/min to achieve the transparency. Vinyl chloride resin paste () was heated to gel. After that, the foam is passed through a heating furnace set at 190℃ at a speed of 1.1 to 1.4 m/min to a total thickness of 2.2 to 2.5 m/m immediately after foaming. Embossing was performed using an electroforming embossing roll with a wood grain design and heating with an electric heater (heating conditions such that the foam layer did not undergo secondary foaming). gap) from 1.9 to 2.1 m/
m, embossing roll pressure: 2Kg/cm ² (gauge pressure)). The results are shown in Table-2. As is clear from Table 2, when the average degree of polymerization of the vinyl chloride resin used in the foamable vinyl chloride resin paste composition is 1210 and 1455, embossing can be performed without problems by setting appropriate embossing conditions. The resulting tuned embossed sheet had a delicate wood grain design similar to natural wood and was suitable as a flooring material.

【table】

【table】

[Table] Examples 3 to 4, Comparative Examples 2 to 3 0.68 m/m thick inorganic filler paper containing glass fiber, pulp, inorganic filler, and binder as main components using a test coater with an effective mechanical width of 450 m/m The foamable vinyl chloride resin pastes (D) to (E) listed in Table 3 were applied to the surface of the
The foamable vinyl chloride resin pastes (D) to (E) were applied to a thick layer and passed through a heating furnace set at 165° C. at a speed of 2 m/min to heat and gel them. Multicolor gravure printing with a wood grain pattern is applied to this surface (the joints corresponding to the joints between wooden boards are printed with printing ink containing a suppressant), and then transparent chloride as listed in Table 3 is applied. Use a doctor knife to combine vinyl resin pastes (A) to (C) as shown in Table 4.
The transparent vinyl chloride resin pastes (A) to (C) were applied to a thickness of m/m and heated to gel by passing through a heating furnace at a rate of 2 m/min at a temperature of 165°C. Then 195℃
The total thickness immediately after foaming (immediately after exiting the foaming furnace) is 1.9 to 2.1.
Heating embossing was carried out using an electric heater using an electroforming embossing roll with a wood grain design similar to that of natural wood using an embossing device installed in-line immediately after the heating furnace. (Electric heater: heating conditions such that the foam layer does not undergo secondary foaming, clearance between embossing roll and back-up roll: 0 (none), embossing roll pressure: 2 Kg/cm ² (gauge pressure)). The results are shown in Table-4.

【table】

【table】

[Table] As is clear from Table 4, the average degree of polymerization of the vinyl chloride resin used in the foamable vinyl chloride resin paste composition is 1455, and the chloride used in the transparent vinyl chloride resin layer formed through printing The average degree of polymerization of the vinyl resin is higher than the average degree of polymerization of the vinyl chloride resin used in the foamable vinyl chloride resin paste composition.
By using a foam with a foaming ratio higher than 100, air bubbles will be generated at the interface between the foam layer and the transparent layer, and the transparency and surface smoothness will not deteriorate, and by setting the foaming ratio to about 2 times or less, it can be used as an embossing roll. Even if the clearance with the back-up roll is 0 (without creating a gap), the embossing work can be carried out without any problems because the foamed gel is not destroyed by the pressure of the embossing roll, and the resulting synchronous embossed sheet resembles natural wood. It was fibrous and had a sharp wood grain pattern, making it suitable for flooring.

Claims (1)

[Claims] 1 A layer of a foamable vinyl chloride resin composition is formed on a base material, an arbitrary pattern is printed on the surface of the layer with a printing ink containing a foaming inhibitor, and a transparent or translucent vinyl chloride resin layer is placed on top of the layer. In a method for manufacturing a synchronized embossed sheet in which the printed pattern and the uneven pattern match, which is formed by heating and foaming to reveal an uneven pattern, and then using an embossing roll with an arbitrary design on the surface to form a squeeze pattern. , the average degree of polymerization of the vinyl chloride resin used in the layer of the foamable vinyl chloride resin composition is 1200 or more, and the average degree of polymerization of the vinyl chloride resin used in the transparent or translucent vinyl chloride resin layer is A method for producing a tuned embossed sheet, characterized in that the degree of polymerization is 100 or more higher than the average degree of polymerization of the vinyl chloride resin used in the layer of the foamable vinyl chloride resin composition, and the expansion ratio is 4 times or less. .